Orange-red to bluish-red mordant dyestuffs and process of making same.



. 1W0 Drawing.

UNITED STAflES PATENT orrion.

CHARLES LA HARPE ANDERNST BODMER, OF BASEL, SWITZERLAND, ASSIGNORS TO DYE WORKS FORMERLY L. DUB/AND, HUGUENIN & CO., 0F BASEL, SWITZERLAND.

ORANGE-RED TO.BLUI SH-RED MORDANT DYESTUFFS AND PROCESS OF'MAKING SAKE.

citizens of theSwiss Republic, and residents "of Basel, Switzerland, .have invented new Orange-Red to Bluish-Red Mordant Dyestutfs and a Process of Making Same, of

which thefollowilig is a full, clear, and exact specification.

We have found that new bluish red mordant nitro-rhodol dyestufis are obtained .by condensing an amino-metaoxybenzoylbenzoic acid substituted in the amino group with nitrated resorein compoundsas, for instanoey nitroresorcin, nitroresorcinsulfonic acids or the sulfonic; acid of nitro-b -resorcylic acid and transfiorming the product thus obtained. into serviceable form by transforming itinto an easily soluv 'ble alkali metal. salt, Thef'new dyestuffs which are thus produced are,jlike the-analogous, "not nitrated rhodols', mordant dye} dyeingson'not mordat'ited' and mordanted rfibeni Their tints on chrome mordanted fiber vary'from orange red to bluish} red In distinction from the wcorresponding not I litrated" rhodols; the Initro-rhodols dye/the, fiber more 'yellowishtint's; Certain prop ertiesof fastness are'favorably afi'ected by the entry ofthe nitro group, such as the 'fastnes's to lightl of the dyeings with chrome inorda-nts on w0ol;'which is better than that of the corresponding not; nitrated 'rhodol s The new dyestuifsare brown to red pow ders, which are easily soluble in water and from these solutions the cv o'rrespending acid nitrorho'dols are precipitated by'adding acid.

.Some of the not sulfonated nitro rhodols group are particularly easily sulfon'ated.

The invention is illustrated by'the follow-.

in exam les, the parts being by weight: Xamp e1: 11 parts of resorcin are dis solved in 120 parts of concentrated sulfuric acid and sulfonated; the mixture is then Specification pt Letters Patent.

7 Application filed luly 8, 1912. Serial No. 708,238,

CHARLES DE LA orange-red to Patented Mar. 11,1913.

nitrated to nitro-resorcin-disulfonie acid corresponding probably to the formula according to the process described in Ger man Patent Specification 145190 'with 14.3 parts of 'a mixture of nitric acid andsulfuric the mass are stirred 28.5 parts of dimethylamino'meta-oxybenzoylbenzoic acid corresponding to the formula (CH:)aN Q H I l e. f

or an equivalent quantity of another N- benzoylbe'nzoic acid, and -.the mixture, as homogeneous as. possible, is heated at 90 until no further increase of dye's'tuif formation can be observed. Thefcooled ina'ss' -is poured into ice-water.-..The' dyestuilseparates in flocks; it is filteredand pressed. By means of sodium acetate solution it canbe dissolved away from impurities which dilute alkalis it dissolves to yellowish rose 60 acid containing 44 per. cent. of H NO Into "15v substitution derivativeof amino-metaeoxyv mmm fil owg Example II: Into a solution of the sulfonic acid of 6-r esorcylic acid made from 16 parts of -resorcylic acid and 64 parts of sulfuric, acid monohydrate, are introduced gradually while stirring well and coolin 18 parts of a mixture of nitric acid and sul uric acid containing 35 per cent. -HNO corresponding with 6.3 parts of nitric acid. The whole is allowed to stand for a long time at the ordinary temperature and finally heated for a short time at 70. After it has been ascertained that free nitric acid is no longer present there are stirred into the cooled mass 28.5 parts of dimethylamino-meta-oxybenzoyllbenzoic acid corresponding to .the formu a v W0 i /W 'coon and the mixture; as homogeneous as possible, is heated at" 90 until no further increase of, the dyestuif formation can be observed. The product is worked up as usual.

- by pouring into ice-water, filtering and pressing the,d yestuff, dissolving away the latter from by-products by means of sodium acetate solution; transforming the dyestufi which has been re-precipitated by acid into a soluble form by dissolving in alkali and salting out.

The dyest-uff 'dyes unmordantcd wool bri ht vred and chrome mordanted wool of green fluorescence.

It corresponds probably to the formula amino-m oxybenzoylbenzoic' acidsubstituted in the amino group with anitrated resorcin compound an t ran s'forming the condensation product thus obtained into an alkali salt.

forming the condensation product thus obtained into an alkali salt.

3. The described process for the manufac' ture of orange-red to bluish-red mordant dyestuffs, which consists in condensing a dialkylamino-m-oxybenzoylbenzoic acid with a nitrated resorcin compound and-transforrning the condensation tained into an alkali salt 4. As new products the described 'nitro' product thus ob rhodol dyestuffs, being alkali metal salts of the condensation products of a nitrated resorcin' compound with an amino-meta-oxybenzoylbenzoic acid substituted intlie amino group and constituting in dry state brown -to red powders easily'soluble in water, soluble in concentrated sulfuric acid with yellow coloration turning to yellowish red-on addition of water, dissolving in dilute alkalis to yellowish rose to rose solutions of green fluorescence and dyeing chrome mordanted fibers orange red to bluish red tints.

Inwitness whereof we have hereunto signed our names this 24th day of June 1912, in the presence of two subscribing witnesses.

CHARLES DE LA HARPE. ERNST BODMER. Witnesses:

, GEO. GIFFORD,

ARMANI) BITTER. 

